Coated Article With Dark Color

ABSTRACT

An article is coated with a coating having a dark color. In a preferred embodiment, the coating comprises a nickel or polymer basecoat layer, and a first color layer comprised of oxygen-rich refractory metal oxycarbides, a second color layer comprising oxygen-rich refractory metal oxycarbides and a top layer of refractory metal oxides.

FIELD OF THE INVENTION

This invention relates to articles, particularly articles such asfaucets, having a decorative and protective coating having theappearance of a dark color. More specifically, the dark color is black,dark bronze, blue-black, vivid blue or a blue-grey color.

BACKGROUND OF THE INVENTION

Current industry practice with various brass articles such as faucets,faucet escutcheons, door knobs, door handles, door escutcheons and thelike, is to first buff and polish the surface of the article to a highgloss and to then apply a protective organic coating, such as onecomprised of acrylics, urethanes, epoxies and the like, onto thispolished surface. This system has the drawback that the buffing andpolishing operation, particularly if the article is of a complex shape,is labor intensive. Also, the known organic coatings are not always asdurable as desired, and are susceptible to attack by acids. It would,therefore, be quite advantageous if brass articles, or indeed otherarticles, either plastic, ceramic, or metallic, could be provided withcoating which provided the article with a decorative appearance as wellas providing wear resistance, abrasion resistance and corrosionresistance.

U.S. Pat. No. 7,270,895 represents a recent development in thistechnology. The patent discloses an article coated with a layer coatinghaving a dark color. Preferably, the color is dark gray or a dark bronzecolor. The coating comprises a color and protective layer comprised of arefractory metal oxycarbide wherein the oxygen content is greater thanthe carbon content. The refractory metal typically is zirconium.

U.S. Pat. No. 8,007,928 represents another recent development in thistechnology. The patent discloses an article coated with a layer coatinghaving a black color. The coating comprises a second color layercomprised of a refractory metal oxycarbide wherein the oxygen content isgreater than the carbon content and a third layer comprised of arefractory metal oxide. The search for novel appearances not previouslyachievable continues.

SUMMARY OF THE INVENTION

The present invention is directed to an article having a dark color. Apreferred coated article has a black color and comprises a substratehaving a surface and having on at least a portion of the surface amulti-layer coating comprising in order:

a first layer of a refractory metal oxycarbide having an oxygen contentand a carbon content wherein the oxygen content is greater than thecarbon content wherein the refractory metal oxycarbide of the firstcolor layer is 20 to 35 atomic percent oxygen, 10 to 20 atomic percentcarbon and 50 to 70 atomic percent refractory metal, a second colorlayer on top of the first color layer;

wherein the second color layer comprises a layer of refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content; and

wherein the oxygen content of the second color layer is greater than theoxygen content of the first color layer wherein the refractory metaloxycarbide of the second color layer is 40 to 65 atomic percent oxygen,5 to 20 atomic percent carbon and 25 to 50 atomic percent refractorymetal; and a refractory metal oxide layer on top of the second colorlayer.

In another preferred embodiment, the coated article has a dark color(black, dark bronze, blue-black) comprising:

a substrate having a surface and having on at least a portion of thesurface a multi-layer coating comprising in order; a first layer of arefractory metal oxycarbide having an oxygen content and a carboncontent wherein the oxygen content is greater than the carbon contentwherein the refractory metal oxycarbide of the first color layer is 20to 35 atomic percent oxygen, 10 to 20 atomic percent carbon and 50 to 70atomic percent refractory metal,

a second color layer on top of the first color layer, wherein the secondcolor layer comprises a layer of refractory metal oxycarbide having anoxygen content and a carbon content wherein the oxygen content isgreater than the carbon content; and wherein the oxygen content of thesecond color layer is greater than the oxygen content of the first colorlayer wherein the refractory metal oxycarbide of the second color layeris 40 to 65 atomic percent oxygen, 5 to 20 atomic percent carbon and 25to 50 atomic percent refractory metal; and a refractory metal oxidelayer on top of the second color layer.

This embodiment encompasses dark bluish and bronze shades as well asblack. The general coating compositions are the same, but layerthicknesses are modified to achieve different color shades.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional view, not to scale, of a portion of thesubstrate having the black color of this invention thereon.

FIG. 2 is a view of FIG. 1 without top layer 20.

FIG. 3 shows second color layer 18 comprising a multiplicity ofalternating layers.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to an article such as a plastic,ceramic, cermet or metallic article having the decorative and protectivecoating deposited on at least a portion of its surface. Moreparticularly, it is directed to an article or substrate, particularly ametallic article such as stainless steel, aluminum, brass or zinc,having deposited on its surface the layers described herein. The coatingis decorative and also provides corrosion resistance, wear resistanceand abrasion resistance. The coating provides the appearance of a blackcolor.

A preferred coated article has a black color and comprises a substratehaving a surface and having on at least a portion of the surface amulti-layer coating comprising in order:

a first layer of a refractory metal oxycarbide having an oxygen contentand a carbon content wherein the oxygen is greater than the carboncontent wherein the refractory metal oxycarbide of the first color layeris 20 to 35 atomic percent oxygen, 10 to 20 atomic percent carbon and 50to 70 atomic percent refractory metal, a second color layer on top ofthe first color layer;

wherein the second color layer comprises a layer of refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content; and

wherein the oxygen content of the second color layer is greater than theoxygen content of the first color layer wherein the refractory metaloxycarbide of the second color layer is 40 to 65 atomic percent oxygen,5 to 20 atomic percent carbon and 25 to 50 atomic percent refractorymetal; and a refractory metal oxide layer on top of the second colorlayer.

Generally, the refractory metal oxide top layer is hafnium, tantalum,zirconium or titanium oxide. Preferably the refractory metal oxide toplayer is zirconium oxide.

FIG. 1 shows Article 10 comprising substrate 12. Substrate 12 can becomprised of any material onto which a plated layer can be applied, suchas plastic, e.g., ABS, polyolefin, polyvinylchloride, andphenolformaldehyde, ceramic, cermet, metal or metal alloy. In oneembodiment it is comprised of a metal or metallic alloy such as copper,steel, brass, zinc, aluminum, nickel alloys and the like.

In the instant invention, as illustrated in FIG. 1, a first layer orseries of layers is applied onto the surface of the article by platingsuch as electroplating in the case of a nickel basecoat. In the case ofa polymeric basecoat, the polymer is applied by conventional means. Asecond series of layers is applied onto the surface of the basecoatlayer or layers by vapor deposition. The polymer or electroplated layersserve, inter alia, as a base coat which levels the surface of thearticle and as a corrosion barrier to improve corrosion resistance. Inone embodiment of the instant invention a nickel layer 14 may bedeposited on the surface of the article. The nickel layer may be any ofthe conventional nickels that are deposited by plating, e.g., brightnickel, semi-bright nickel, satin nickel, etc. Nickel layer 14 may bedeposited on at least a portion of the surface of the substrate 12 byconventional and well-known electroplating processes. Layer 14 may beone or more layers of copper, nickel and chromium. These corrosionprotective layers are well known in the art.

Layer 14 may be comprised of a polymer applied onto the surface ofarticle 10 as a basecoat layer. A second series of layers is appliedonto the surface of the polymeric layer by vapor deposition. Thepolymeric layer serves, inter alia, as a base coat which levels thesurface of the article and as a corrosion barrier to improve corrosionresistance. In the instant invention polymeric layer 14 is deposited onthe surface of the article.

Polymeric basecoat layer 14 may be comprised of both thermoplastic andthermoset polymeric or resinous material. These polymeric or resinousmaterials include the well known, conventional and commerciallyavailable polycarbonates, epoxy urethanes, polyacrylates,polymethacrylates, nylons, polyesters, polypropylenes, polyepoxies,alkyds and styrene containing polymers such as polystyrene,styrene-acrylonitrile (SAN), styrene-butadiene,acrylonitrile-butadiene-styrene (ABS), and blends and copolymersthereof. The polymers for layer 14 are well known in the art.

Over layer 14 is deposited, by vapor deposition such as physical vapordeposition or chemical vapor deposition, protective and decorative colorlayer 16. Color layer 16 is comprised of a layer refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than carbon content.

Second color layer 18 is deposited on top of first color layer 16.Second color layer 18 comprises a layer of refractory metal oxycarbidehaving an oxygen content and a carbon content wherein the oxygen contentis greater than the carbon content; and wherein the oxygen content andthe carbon content of second color layer 18 is greater than the oxygencontent and the carbon content of first color layer 16.

The thickness of color and protective layers 16 and 18 are of athickness which is at least effective to provide the color of dark grayand to provide abrasion resistance, scratch resistance, and wearresistance. Generally, this thickness is at least about 1,000 Å,preferably at least about 1,500 Å, and more preferably at least about2,500 Å. The upper thickness range is generally not critical and isdependent upon secondary considerations such as cost. Generally athickness of about 7500 Å, preferably about 5000 Å should not beexceeded.

Layers 16 and 18 are deposited by conventional and well known techniquesincluding vapor deposition techniques such as cathodic arc evaporation(CAE) or sputtering, and the like. Sputtering and CAE techniques andequipment are disclosed, inter alia, in J. Vossen and W. Kern “Thin FilmProcesses II”, Academic Press, 1991; R. Boxman et al, “Handbook ofVacuum Arc Science and Technology”, Noyes Pub., 1995; and U.S. Pat. Nos.4,162,954 and 4,591,418, all of which are incorporated herein byreference.

One method of depositing layers 16 and 18 are by physical vapordeposition utilizing reactive sputtering or reactive cathodic arcevaporation. Reactive cathodic arc evaporation and reactive sputteringare generally similar to ordinary sputtering and cathodic arcevaporation except that a reactive gas is introduced into the chamberwhich reacts with the dislodged target material.

Next, refractory metal oxide layer 20 is deposited on top of secondcolor layer 18. The refractory metal oxides include oxides of hafnium,tantalum, zirconium, titanium and titanium-zirconium alloys. Generally,this thickness of layer 20 is at least about 60 Å, preferably at leastabout 120 Å, and more preferably about 250 Å.

Layer 20 is deposited by conventional and well known vapor depositiontechniques including physical vapor deposition techniques such ascathodic arc evaporation (CAE) or sputtering. Briefly, in the sputteringdeposition process a refractory metal (such as titanium or zirconium)target, which is the cathode, and the substrate are placed in a vacuumchamber. The air in the chamber is evacuated to produce vacuumconditions in the chamber. An inert gas, such as Argon, is introducedinto the chamber. The gas particles are ionized and are accelerated tothe target to dislodge titanium or zirconium atoms. The dislodged targetmaterial is then typically deposited as a coating film on the substrate.

In cathodic arc evaporation, an electric arc of typically severalhundred amperes is struck on the surface of a metal cathode such aszirconium or titanium. The arc vaporizes the cathode material, whichthen condenses on the substrates forming a coating.

In another preferred embodiment, the article of FIG. 1 has a black, darkbronze or blue-black color. This embodiment is a substrate having asurface and having on at least a portion of the surface a multi-layercoating comprising in order; a first layer of a refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content wherein the refractorymetal oxycarbide of the first color layer is 20 to 35 atomic percentoxygen, 10 to 20 atomic percent carbon and 50 to 70 atomic percentrefractory metal,

a second color layer on top of the first color layer, wherein the secondcolor layer comprises a layer of refractory metal oxycarbide having anoxygen content and a carbon content wherein the oxygen content isgreater than the carbon content; and wherein the oxygen content of thesecond color layer is greater than the oxygen content of the first colorlayer wherein the refractory metal oxycarbide of the second color layeris 40 to 65 atomic percent oxygen, 5 to 20 atomic percent carbon and 25to 50 atomic percent refractory metal; and a refractory metal oxidelayer on top of the second color layer.

This embodiment encompasses bluish and bronze shades as well as black.The general coating compositions are the same, but layer thicknesses aremodified to achieve different color shades.

FIG. 2 shows an article having a blue-grey color that does not use allthree color layers, but just the first and second color layer with notop layer 20.

The coated article has a blue-grey color comprising a substrate having asurface and having on at least a portion of the surface a multi-layercoating comprising in order: a first layer of a refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content wherein the refractorymetal oxycarbide of the first color layer is 20 to 35 atomic percentoxygen, 10 to 20 atomic percent carbon and 50 to 70 atomic percentrefractory metal, a second color layer on top of the first color layer,wherein the second color layer comprises a layer of refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content; and wherein theoxygen content of the second color layer is greater than the oxygencontent of the first color layer wherein the refractory metal oxycarbideof the second color layer is 40 to 65 atomic percent oxygen, 5 to 20atomic percent carbon and 25 to 50 atomic percent refractory metal.

Preferably the refractory metal oxycarbide of the first color layer is15 atomic percent carbon and 25 to 30 atomic percent oxygen.

Preferably the refractory metal oxycarbide of the second color layer is10 atomic percent carbon and 50 to 60 atomic percent oxygen.

FIG. 3 shows how to achieve a vivid blue color by alternating or pulsingbetween the top two layers many times at short durations. FIG. 3 showssecond color layer 18 having layers 22, 24, 26, and 28. The number oflayers in second color layer 18 may vary widely. The number of layersmay range from 2 to 60. Preferably the number ranges from 2 to 30 andmore preferably from 2 to 10. The thickness of each layer of secondcolor layer 18 may vary.

In one embodiment, refractory metal oxide top layer 20 comprisesalternating layers in much the same fashion as second color layer 18.

The coated article has a vivid blue color comprising a substrate havinga surface and having on at least a portion of the surface a multi-layercoating comprising in order: a first layer of a refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content wherein the refractorymetal oxycarbide of the first color layer is 20 to 35 atomic percentoxygen, 10 to 20 atomic percent carbon and 50 to 70 atomic percentrefractory metal, a second color layer on top of the first color layer,wherein the second color layer comprises alternating layers between alayer of refractory metal oxycarbide having an oxygen content and acarbon content wherein the oxygen content is greater than the carboncontent; and wherein the oxygen content of the second layer is greaterthan the oxygen content of the first color layer wherein the refractoryoxycarbide of the second color layer is 40 to 65 atomic percent oxygen,5 to 20 atomic percent carbon and 25 to 50 atomic percent refractorymetal; and a refractory metal oxide layer. The number of alternatinglayers in this second color layer may range between 4 and 60.Preferably, the range is 4 to 20 layers.

The refractory metal of the first color layer is hafnium, tantalum,zirconium, titanium or zirconium-titantium alloy.

The refractory metal oxycarbide of the first color layer is 15 atomicpercent carbon and 25 to 30 atomic percent oxygen.

The refractory metal oxycarbide of the second color layer is 10 atomicpercent carbon and 50 to 60 atomic percent oxygen.

The refractory metal oxide top layer is hafnium, tantalum, zirconium ortitanium oxide.

Preferably, the refractory metal oxide top layer is zirconium oxide.

The first layer of this article has a dark gray color.

The first layer is a thicker than alternating layers comprising thesecond layer.

In order that the invention may be more readily understood, thefollowing example is provided. The example is illustrative and does notlimit the invention thereto.

EXAMPLE I

Brass faucets are placed in a conventional soak cleaner bath containingthe standard and well known soaps, detergents, defloculants and the likewhich is maintained at a pH of 8.9-9.2 and a temperature of 180-200° F.for about 10 minutes. The brass faucets are then placed in aconventional ultrasonic alkaline cleaner bath. The ultrasonic cleanerbath has a pH of 8.9-9.2, is maintained at a temperature of about160-180° F., and contains the conventional and well known soaps,detergents, defloculants and the like. After the ultrasonic cleaning thefaucets are rinsed and placed in a conventional alkaline electro cleanerbath.

The electro cleaner bath is maintained at a temperature of about140-180° F., a pH of about 10.5-11.5, and contains standard andconventional detergents. The faucets are then rinsed twice and placed ina conventional acid activator bath. The acid activator bath has a pH ofabout 2.0-3.0, is at an ambient temperature, and contains a sodiumfluoride based acid salt. The faucets are then rinsed twice and placedin a bright nickel plating bath for about 12 minutes. The bright nickelbath is generally a conventional bath which is maintained at atemperature of about 130-150° F., a pH of about 4.0, contains NiSO₄,NiCl₂, boric acid, and brighteners. A bright nickel layer of an averagethickness of about 10 μm is deposited on the faucet surface.

The bright nickel plated faucets are rinsed three times and then placedin a conventional, commercially available hexavalent chromium platingbath using conventional chromium plating equipment for about sevenminutes. The hexavalent chromium bath is a conventional and well knownbath which contains about 32 ounces/gallon of chromic acid. The bathalso contains the conventional and well known chromium platingadditives. The bath is maintained at a temperature of about 112°-116°F., and utilizes a mixed sulfate/fluoride catalyst. The chromic acid tosulfate ratio is about 200:1. A chromium layer of about 0.25 μm isdeposited on the surface of the bright nickel layer. The faucets arethoroughly rinsed in deionized water and then dried.

The chromium plated faucets are placed in a cathodic arc evaporationplating vessel. The vessel is generally a cylindrical enclosurecontaining a vacuum chamber which is adapted to be evacuated by means ofpumps. A source of argon gas is connected to the chamber by anadjustable valve for varying the rate of flow of argon into the chamber.In addition, sources of methane and oxygen gases are connected to thechamber by adjustable valves for varying the flow rates of methane andoxygen into the chamber.

A cylindrical cathode is mounted in the center of the chamber andconnected to negative outputs of a variable D.C. power supply. Thepositive side of the power supply is connected to the chamber wall. Thecathode material comprises zirconium.

The plated faucets are mounted on spindles, of which are mounted on aring around the outside of the cathode. The entire ring rotates aroundthe cathode while each spindle also rotates around its own axis,resulting in a so-called planetary motion which provides uniformexposure to the cathode for the multiple faucets mounted around eachspindle. The ring typically rotates at several rpm, while each spindlemakes several revolutions per ring revolution. The spindles areelectrically isolated from the chamber and provided with rotatablecontacts so that a bias voltage may be applied to the substrates duringcoating.

The vacuum chamber is evacuated to a pressure of about 10⁻⁵ to 10⁻⁷ torrand heated to about 150° C.

The electroplated faucets are then subjected to a high-bias arc plasmacleaning in which a (negative) bias voltage of about −600 volts isapplied to the electroplated faucets while an arc of approximately 500amperes is struck and sustained on the cathode. The duration of thecleaning is approximately five minutes.

Zirconium oxycarbide color layer 16 now is deposited. Flows of argon andmethane are introduced into the vacuum chamber while the arc dischargecontinues at approximately 500 amperes. In order to increase thedarkness of the coating, a flow of oxygen, amounted to 30 to 40 percentof the total gas flow, may also be introduced into the chamber toproduce the dark gray color. The flow rate of methane is adjusted suchthat the resulting layer contains a carbon content between 10 to 20atomic percent.

Next zirconium oxycarbide color layer 18 is deposited on layer 16. flowsof argon and methane are introduced into the vacuum chamber while thearc discharge continues at approximately 500 amperes. In order toincrease the darkness of the coating, a flow of oxygen, amounted to 30to 40 percent of the total gas flow, may also be introduced into thechamber to produce the dark gray color. The flow rate of methane isadjusted such that thus the resulting layer contains a carbon contentbetween 10 to 20 atomic percent. After this zirconium oxycarbide layeris deposited, the flow of oxygen of approximately 100 to 500 standardliters per minute is introduced for a time of about 10 to 60 seconds. Athin layer of zirconium oxide with a thickness of about 20 to 100 Å isformed. The arc is extinguished, the vacuum chamber is vented and thecoated articles removed.

After this zirconium oxycarbide layer is deposited, the flow of oxygenof approximately 100 to 500 standard liters per minute is introduced fora time of about 1 to 5 minutes. A thin layer of zirconium oxide with athickness of about 100 to 1000 Å is formed. A layer of zirconium oxide(top layer 20) having an average thickness of about 0.1 μm is depositedduring a one to five minute period. The arc is extinguished, the vacuumchamber is vented and the coated articles removed. The cathodic arcdeposition process comprises applying D.C. power to the cathode toachieve a current flow of about 500 amps, introducing argon gas into thevessel to maintain the pressure in the vessel at about 1 to 5 millitorrand rotating the faucets in a planetary fashion described above.

EXAMPLE II

In Example I, the end colors for layers 16 and 18 were in the colorranges for gray and bronze. These were measured on a colorspectrophotometer using a D65 illuminant.

As is known, the measurement of color is determined by three specificparameters in which “L” is a measure of the lightness of an object, “a”is a measure of the redness (positive) or greenness (negative), and “b”is a measure of yellowness (positive) or blueness (negative). Thesethree parameters, together, define a specific color.

The measured black color of Article 10 fell within the following ranges.

Article 10 Black:

L*=35.0+/−5.0

a*=0.00+/−2.0

b*=0.00+/−3.0

The base layer has a gray color, zirconium oxycarbide is preferred. Thenext layer is also a zirconium oxycarbide, but is deposited with higheroxygen and carbon content. This layer darkens the appearance and has theeffect of optically canceling out the yellow normally seen in the toplayer, which is zirconium oxide. The combined properties of these threelayers result in a much darker, blacker appearance than achievablepreviously.

EXAMPLE III

The measured grey-blue color of the embodiment show in FIG. 2 fellwithin the following ranges:

L*=45.0±5.0

a*=−2.0±2.0

b*=−5.0±4.0

The thickness of the second color topmost ZrOC layer 18, ranges between30-60 nm. The base layer, the first color layer, can be 0.1 to 3 microns(or thicker), preferably 0.5 microns. This embodiment does not have toplayer 20.

EXAMPLE IV

The measured, vivid blue color of the embodiment shown in FIG. 3 fellwithin the ranges:

L*=40.0±5.0

a*=−3.0±3.0

b*=−25.0±5.0

For the thicknesses of the individual alternating layers of second colorlayer 18 range between 2-10 nm thick layers. The first color layer 16ranges from 0.1 to 3 microns (or thicker), preferably 0.5 microns.

While certain embodiments of the invention have been described forpurposes of illustration, it is to be understood that there may bevarious embodiments and modifications within the general scope of theinvention.

1. A coated article having a black color comprising a substrate having asurface and having on at least a portion of the surface a multi-layercoating comprising in order: a first layer of a refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content wherein the refractorymetal oxycarbide of the first color layer is 20 to 35 atomic percentoxygen, 10 to 20 atomic percent carbon and 50 to 70 atomic percentrefractory metal, a second color layer on top of the first color layer,wherein the second color layer comprises a layer of refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content; and wherein theoxygen content of the second color is greater than the oxygen content ofthe first color layer wherein the refractory metal oxycarbide of thesecond color layer is 40 to 65 atomic percent oxygen, 5 to 20 atomicpercent carbon and 25 to 50 atomic percent refractory metal; and arefractory metal oxide layer on top of the second color layer; whereinthe first layer has a dark gray color, the second layer has a dark praycolor, the top layer has a yellow color and the article has a blackcolor.
 2. The article of claim 1 wherein the refractory metal of thefirst color layer is hafnium, tantalum, zirconium, titanium orzirconium-titanium alloy.
 3. The article of claim 1 wherein therefractory metal of the first color layer is zirconium.
 4. The articleof claim 1 wherein the refractory metal oxycarbide is of the first colorlayer zirconium oxycarbide.
 5. The article of claim 1 wherein therefractory metal oxycarbide of the first color is 15 atomic percentcarbon and 25 to 30 percent atomic percent oxygen.
 6. The article ofclaim 1 wherein the refractory metal of the second color layer ishafnium, tantalum, zirconium, titanium or zirconium-titanium alloy. 7.The article of claim 1 wherein the refractory metal of the second colorlayer is zirconium.
 8. The article of claim 1 wherein the refractorymetal oxycarbide is of the second color layer zirconium oxycarbide. 9.The article of claim 1 wherein the refractory metal oxycarbide of thesecond color layer is 10 atomic percent carbon and 50 to 60 atomicpercent oxygen.
 10. The article of claim 1 wherein the refractory metaloxide top layer is hafnium, tantalum, zirconium or titanium oxide. 11.The article of claim 1 wherein the refractory metal oxide top layer iszirconium oxide.
 12. (canceled)
 13. The article of claim 1 wherein thefirst layer is a thicker than, the second layer and wherein the firstlayer is thicker than the top layer.
 14. A coated article having a darkcolor comprising a substrate having a surface and having on at least aportion of the surface a multi-layer coating comprising in order: afirst layer of a refractory metal oxycarbide having an oxygen contentand a carbon content wherein the oxygen content is greater than thecarbon content wherein the refractory metal oxycarbide of the firstcolor layer is 20 to 35 atomic percent oxygen, 10 to 20 atomic percentcarbon and 50 to 70 atomic percent refractory metal, a second colorlayer on top of the first color layer, wherein the second color layercomprises a layer of refractory metal oxycarbide having an oxygencontent and a carbon content wherein the oxygen content is greater thanthe carbon content; and wherein the oxygen content of the second coloris greater than the oxygen content of the first color layer wherein therefractory metal oxycarbide of the second color layer is 40 to 65 atomicpercent oxygen, 5 to 20 atomic percent carbon and 25 to 50 atomicpercent refractory metal; and a refractory metal oxide layer on top ofthe second color layer; wherein the first layer has a dark gray color,the second layer has a dark gray color, the top layer has a yellow colorand the article has a black, dark bronze or blue-black color. 15.(canceled)
 16. The article of claim 14 wherein the refractory metaloxycarbide of the first color layer is 15 atomic percent carbon and 25to 30 atomic percent oxygen.
 17. The article of claim 14 wherein therefractory metal oxycarbide of the second color layer is 10 atomicpercent carbon and 50 to 60 atomic percent oxygen.
 18. (canceled) 19.The article of claim 14 wherein the first layer is a thicker than, thesecond layer and wherein the first layer is thicker than the top layer.20. A coated article having a blue-grey color comprising a substratehaving a surface and having on at least a portion of the surface amulti-layer coating comprising in order: a first layer of a refractorymetal oxycarbide having an oxygen content and a carbon content whereinthe oxygen content is greater than the carbon content wherein therefractory metal oxycarbide of the first color layer is 20 to 35 atomicpercent oxygen, 10 to 20 atomic percent carbon and 50 to 70 atomicpercent refractory metal, a second color layer on top of the first colorlayer, wherein the second color layer comprises a layer of refractorymetal oxycarbide having an oxygen content and a carbon content whereinthe oxygen content is greater than the carbon content; and wherein theoxygen content of the second color is greater than the oxygen content ofthe first color layer wherein the refractory metal oxycarbide of thesecond color layer is 40 to 65 atomic percent oxygen, 5 to 20 atomicpercent carbon and 25 to 50 atomic percent refractory metal.
 21. Thearticle of claim 20 wherein the refractory metal oxycarbide of the firstcolor layer is 15 atomic percent carbon and 25 to 30 atomic percentoxygen.
 22. The article of claim 20 wherein the refractory metaloxycarbide of the second color layer is 10 atomic percent carbon and 50to 60 atomic percent oxygen.
 23. A coated article having a vivid bluecolor comprising a substrate having a surface and having on at least aportion of the surface a multi-layer coating comprising in order: afirst layer of a refractory metal oxycarbide having an oxygen contentand a carbon content wherein the oxygen content is greater than thecarbon content wherein the refractory metal oxycarbide of the firstcolor layer is 20 to 35 atomic percent oxygen, 10 to 20 atomic percentcarbon and 50 to 70 atomic percent refractory metal, a second colorlayer on top of the first color layer, wherein the second color layercomprises a layer of refractory metal oxycarbide having an oxygencontent and a carbon content wherein the oxygen content is greater thanthe carbon content wherein the second color layer comprises amultiplicity of layers; and wherein the oxygen content of the secondcolor is greater than the oxygen content of the first color layerwherein the refractory metal oxycarbide of the second color layer is 40to 65 atomic percent oxygen, 5 to 20 atomic percent carbon and 25 to 50atomic percent refractory metal; and a refractory metal oxide top layer.24. The article of claim 23 wherein the second color layer comprises 2to 30 alternating layers.
 25. The article of claim 23 wherein the secondcolor layer comprises 2 to 10 alternating layers.
 26. The article ofclaim 23 wherein the oxide top layer comprises a multiplicity ofalternating layers.
 27. The article of claim 23 wherein the top layercomprises 2 to 10 alternating layers.
 28. The article of claim 23wherein the refractory metal oxycarbide of the first color layer is 15atomic percent carbon and 25 to 30 atomic percent oxygen.
 29. Thearticle of claim 23 wherein the refractory metal oxycarbide of thesecond color layer is 10 atomic percent carbon and 50 to 60 atomicpercent oxygen.
 30. The article of claim 23 wherein the first layer is athicker than alternating layers comprising the second layer.
 31. Acoated article having a vivid blue color comprising a substrate having asurface and having on at least a portion of the surface a multi-layercoating comprising in order: a first layer of a refractory metaloxycarbide having an oxygen content and a carbon content wherein theoxygen content is greater than the carbon content wherein the refractorymetal oxycarbide of the first color layer is 20 to 35 atomic percentoxygen, 10 to 20 atomic percent carbon and 50 to 70 atomic percentrefractory metal, a second color layer on top of the first color layer,wherein the second color layer comprises a refractory metal oxide. 32.The article of claim 31 wherein the refractory metal oxycarbide of thefirst color layer is 15 atomic percent carbon and 25 to 30 atomicpercent oxygen.
 33. The article of claim 31 wherein the second layer isbetween 25 and 100 nm thick.